Catalysts

ABSTRACT

A catalyst effective for the direct reaction of hydrogen and oxygen to form hydrogen peroxide includes particles of gold, palladium or, preferably, gold and palladium deposited upon an acid-washed support. High selectivity to and production of hydrogen peroxide is observed, with low hydrogen peroxide decomposition. The catalysts have extended lifespan.

The present invention concerns improvements in catalysts especially for hydrogen peroxide production; more especially it concerns the catalytic production of hydrogen peroxide by direct reaction of hydrogen and oxygen.

The standard large scale production method for hydrogen peroxide involves the use of anthraquinone as an intermediate. This process is energy-intensive. There has been considerable study over the last 10 to 15 years of alternative processes for direct oxidation of hydrogen by oxygen, but these have not, to our knowledge, been successfully commercialised. There are understandable concerns over the danger of operating with explosive mixtures of hydrogen and oxygen. As examples of recent publications in this field, we mention in particular U.S. Pat. No. 5,135,731, in which gases containing hydrogen and oxygen are reacted in the presence of an aqueous reaction medium, an acid, a promoter, a multifunctional phosphonate and a catalyst, for example Pd and/or Pt which may be on a support such as carbon, alumina, silica, ion exchange resins and other conventional supports. U.S. Pat. No. 4,832,938 is another concept which involves reacting hydrogen with oxygen in an aqueous reaction medium having no, or less than 2%, organic content, a source of protons and chlorine or bromine ions and a combined Pt/Pd catalyst. The catalyst may be supported on carbon, silica or alumina. U.S. Pat. No. 4,009,252 also describes an aqueous medium system using a platinum group metal catalyst.

More recently, Landon et al have published a paper in Phys. Chem. Chem. Phys. 5 (2003) 917 studying a variety of Au and Pd catalysts, and disclosing that a gold alloy catalyst, specifically 5 wt % Au—Pd (1:1 wt %) supported on alumina is an active catalyst for H₂O₂ formation. Trials were carried out using a reaction medium including supercritical CO₂, but overall yields were low because of H₂O₂ decomposition. Although this academic work is interesting, it seems that high selectivities to H₂O₂ of 80-90% can be achieved at low temperatures of the order of 1-2° C. but only with low overall yields. Such low temperatures result in an energy-intensive process.

Two other patent documents are U.S. Pat. No. 5,449,655 and EP 0 049 810. U.S. Pat. No. 5,449,655 discloses that activated carbon catalyst supports may be acid-washed to reduce the ash content, and that a further treatment is desirable to improve the catalytic performance for hydrogenation of organic molecules after deposition of a platinum group metal on the supports. The further treatment suitably involves treatment with an oxidising agent such as hydrogen peroxide. This document does not have any relevance to the formation of catalysts for hydrogen peroxide formation by direct reaction of hydrogen and oxygen. EP 0 049 810 is concerned with an improvement in hydrogen peroxide production, using a palladium or palladium-gold catalyst supported catalyst, by selecting catalysts that show decreased hydrogen peroxide decomposition. The improved catalyst is prepared by pretreatment of the catalyst with an aldehyde or a ketone and/or hydrochloric acid. The present invention relates not to the pre-treatment of the catalyst before use in the hydrogen peroxide process, but in the pre-treatment of the support, before formation of the catalyst.

There remains a need for a commercially viable catalyst and commercially viable direct reaction process for the production of H₂O₂.

Accordingly, the present invention provides an H₂O₂ formation catalyst comprising particles of gold, palladium or, preferably, gold and palladium, deposited on a support which has been acid washed prior to metal deposition. Preferably the particles are of gold and palladium, which may, on certain supports, have a gold-rich core and a palladium-rich shell.

The support is preferably an inorganic support material, preferably SiO₂, TiO₂, Al₂O₃ or Fe₂O₃, or may be an activated carbon. Acid washing is suitably carried using a mineral acid such as hydrochloric acid or nitric acid. Preferably the acid is dilute nitric acid, and supports are treated for example for 3 hours at ambient temperature. Experimental procedures involved washing supports in various concentrations of acid (see FIG. 1 below). It may be desirable to use a zeolite support, and synthetic zeolites such as beta zeolite or ZSM-5 are indicated, while tests indicate that zeolite Y tends to collapse. deposited on its surface metal nanoparticles where there has been migration of gold towards the core of the nanoparticles and palladium towards the surface of the nanoparticles. Thus a palladium-rich shell surrounds a gold-rich core. Conveniently, the core contains 50 at % or more of gold, and the shell contains 50 at % or more of palladium.

In initial tests, the alloyed catalysts had a 2.5Au-2.5Pd wt % loading, with comparative Au and Pd monometallic catalysts having 2.5 wt % and 5 wt % loadings. Other metal loadings may be considered, especially during catalyst development directed to precious metal “thrifting”.

The present invention further provides a method of manufacture of such a catalyst according to the invention, comprising acid washing a catalyst support, depositing gold and/or palladium, conveniently gold and palladium simultaneously, onto the washed support to form a catalyst precursor, and subsequently heat-treating, preferably at a temperature of 400° C. or above, the catalyst precursor to form a catalyst comprising the gold, palladium or gold and palladium particles.

The present invention also provides a process for the production of H₂O₂, comprising reacting hydrogen with oxygen in the presence of a reaction medium, preferably an aqueous reaction medium, and in the presence of a catalyst according to the invention.

The reaction medium is conveniently a water/organic solvent mix, where the organic solvent is water miscible. Solvents such as methanol, ethanol, isopropyl alcohol and acetone are suitable. In certain tests an acetone/water mix has been found to increase the activity of the bi-metallic catalyst (see Table 1 below). However, studies into different solvents (isopropyl alcohol, ethanol) showed no promotion of the catalyst activity. Studies into solvent effects have to be carried out with due care due to the possible formation of organic peroxy species, but studies by ¹H NMR and ¹³C NMR with acetone and methanol have shown conclusively that under the conditions as stated in Table 1 there is no formation of such species.

TABLE 1 Table 1 Effect of solvent and temperature on H₂O₂ synthesis - all catalysts calcined in air 400° C. 3 hours. H₂O₂ Productivity decomposition ^(a) Catalyst Solvent Temperature/° C. Mol/kg_(cat)/hr % 2.5-2.5%Au—Pd/ Water + Methanol 2 52 nd HZSM-5 2.5-2.5%Au—Pd/ Water + Methanol 2 87 Nd HZSM-5 10%HNO 3 2.5-2.5%Au—Pd/ Water + Methanol 2 64 30 TiO₂ 2.5-2.5%Au—Pd/ Water + Methanol 20 25 70 TiO₂ 2.5-2.5%Au—Pd/ Water + Methanol 2 80 ca 5 TiO₂ 2%HNO₃ 2.5-2.5%Au—Pd/ Water + Methanol 20 100 35 TiO₂ 2%HNO₃ 2.5-2.5%Au—Pd/ Water + Acetone 2 95 13 TiO₂ 2% HNO₃ 2.5-2.5%Au—Pd/ Water + Acetone 20 125 Nd TiO₂ 2% HNO₃ 2.5-2.5%Au—Pd/ Water + Acetone 40 64 Nd TiO₂ 2% HNO₃ Note water is 2.9 g in all cases-solvent 5.6 g Note ^(a) H₂O₂ decomposition experiments; 0.5 wt % H₂O₂ added at start, no O₂

Using the nitric acid washed TiO₂ catalyst results in activity in temperatures 2° C.-40° C. (table 1) without suffering a major loss in activity, in comparison to the non acid washed catalyst.

Other aspects of the present invention are disclosed in the Examples below.

EXAMPLE 1 Comparative

2.5 wt % Au-2.5 wt % Pd catalysts were prepared by impregnation of suitable support materials: carbon (commercially available G60), silica and TiO₂ (mainly anatase). An incipient wetness method using aqueous solutions of PdCl₂ (Johnson Matthey) and HAuCl₄.3H₂O (Johnson Matthey) was employed. The paste formed was ground and dried at 80° C. for 16 h and calcined in static air, typically at 400° C. for 3 h.

10 mg of the supported 2.5 wt % Au-2.5 wt % Pd catalyst were charged in an autoclave containing solvent (5.6 g MeOH and 2.9 g H₂O), which was then filled with 5% H₂/CO₂ and 25% O₂/CO₂ to give a hydrogen to oxygen ratio of 1:2, at a total pressure of 3.7 MPa at 20° C. Stirring (1200 rpm) was started on reaching the desired temperature (2° C.), and experiments were carried out for 30 min. Gas analysis for H₂ and O₂, was performed by gas chromatography using a thermal conductivity detector. Conversion of H₂ was calculated by gas analysis before and after reaction. H₂O₂ yield was determined by titration of aliquots of the final filtered solution with acidified Ce(SO₄)₂ (7×10⁻³ mol/l). Ce(SO₄)₂ solutions were standardised against (NH₄)₂Fe(SO₄)₂.6H₂O using ferroin as indicator. The following results were obtained:

Catalyst Productivity Mol/kg_(cat)-h 2.5%Au2.5%Pd/TiO₂ 64 2.5%Au2.5%Pd/Al₂O₃ 15 2.5%Au2.5%Pd/G60 110 2.5%Au2.5%Pd/SiO₂ 108

EXAMPLE 2

The supports were acid-treated (3 h, 100 ml) prior to impregnation of Au and Pd (as described in Example 1) and hydrogen peroxide synthesis measured as described in Example 1. A reference sample washed for 3 h in pure water was also tested. The following results were obtained:

Selectivity Productivity Catalyst Pre-treatment % Mol/kg_(cat)-h 2.5%Au—2.5%Pd/G60 None 80 110 2.5%Au—2.5%Pd/G60 Water 80 112 2.5%Au—2.5%Pd/G60 2%HNO₃ >98 160 2.5%Au—2.5%Pd/G60 2%H₃PO₄ 30 120 2.5%Au—2.5%Pd/G60 2%HCl 15 130 2.5%Au—2.5%Pd/G60 2%NH₄OH 24 70 2.5%Au—2.5%Pd/G60 2%CH₃COOH >98 175 2.5%Au—2.5%Pd/G60 1N HCl* 20 30 2.5%Au—2.5%Pd/G60 1N HNO₃* 80 110 2.5%Au—2.5%Pd/TiO₂ None 61 64 2.5%Au—2.5%Pd/TiO₂ Water 95 80 2.5%Au—2.5%Pd/SiO₂ None 80 108 2.5%Au—2.5%Pd/SiO₂ Water 73 185 *Catalyst was prepared on untreated carbon with 1N HCl or HNO₃ present during impregnation.

EXAMPLE 3

The solvent and solvent/water composition was varied and hydrogen peroxide synthesis measured (as in Example 1) for the catalysts formed from the G60 acid-treated and water treated supports. All catalysts were calcined in static air 400° C. 3 hrs. The results were as follows:

Productivity Catalyst Pre-treatment Solvent Mol/kg_(cat)-h 2.5-2.5%Au—Pd/TiO₂ Water Methanol/Water 64 2.5-2.5%Au—Pd/TiO₂ 2%HNO₃ Methanol/Water 80 2.5-2.5%Au—Pd/TiO₂ 2%HNO₃ Acetone/water 95 2.5%Au2.5%Pd/G60 Water Methanol/Water* 118 2.5%Au2.5%Pd/G60 2%HNO₃ Methanol/Water* 160 2.5%Au2.5%Pd/G60 Water Ethanol/Water* 100 2.5%Au2.5%Pd/G60 2%HNO₃ Ethanol/Water* 200 2.5%Au2.5%Pd/G60 2%HNO₃ Ethanol/Water** 60 2.5%Au2.5%Pd/G60 Water Water 31 2.5%Au2.5%Pd/G60 2%HNO₃ Water 33 2.5%Au2.5%Pd/TiO₂ Water Water 30 2.5%Au2.5%Pd/TiO₂ 2%HNO₃ Water 32 *74% alcohol by weight, Methanol/Water, Ethanol/Water same molar ratio **5% alcohol by weight

EXAMPLE 4

Examples of the supports and impregnated catalysts were tested for hydrogen peroxide decomposition. All catalysts were calcined in static air 400° C. 3 hr. The following results were obtained:

H₂O₂Productivity Decomposition (%)* Support Pre-treatment (mol/Kg_(cat)-h) catalyst support AC¹ None 110 20 40^(a), 38^(b) AC¹ Water 112 21 39  AC¹ 2%HNO₃ 160 1.8 15^(a), 0^(b)  TiO₂ ² None 64 30 20^(a) TiO₂ ² Water 64 32 20^(a), 19^(b) TiO₂ ² 2%HNO₃ 95 5 0^(a), 0^(b) *Hydrogen peroxide decomposition over 2.5wt%Au—2.5wt%Pd catalyst or the support: H₂O₂ (0.4 wt. %) in a methanol/water solution (CH₃OH, 5.6 g; H₂O 2.9 g) reacted with 420 psi H₂ for 30 min at 2° C. ¹2.5%Au2.5%Pd/G6O activated carbon (Aldrich) ²TiO₂ (P25) ex Degussa ^(a)Decomposition over fresh support ^(b)Decomposition over once-used support ^(a)Decomposition over fresh support ^(b)Decomposition over used support

EXAMPLE 5

The catalyst supports detailed in Example 1 were treated with nitrate salts (sodium, potassium and ammonium) before impregnation with Au and Pd and tested for hydrogen peroxide synthesis (as described in Example 1). All catalysts were calcined in static air 400° C. 3 hr. The following results were obtained:

Productivity Catalyst Pre-treatment Mol/kg_(cat)-h 2.5%Au2.5%Pd/G60 None 118 2.5%Au2.5%Pd/G60 2%HNO₃ 160 2.5%Au2.5%Pd/G60 2%NaNO₃ 122 2.5%Au2.5%Pd/G60 2%KNO₃ 120 2.5%Au2.5%Pd/G60 2%NH₄NO₃ 115

EXAMPLE 6

Hydrogen peroxide synthesis was carried out with a 2.5 wt % Au-2.5 wt % Pd catalyst supported on G60 acid-treated and water treated carbon calcined in air 400° C. 3 hrs air. The autoclave was vented at 30 minute intervals, the hydrogen peroxide concentration measured, and the gas mixture refilled and the synthesis allowed to continue. The results obtained are shown in FIG. 4.

EXAMPLE 7

Hydrogen peroxide synthesis was measured as in Example 1, at various reaction temperatures for a 2.5 wt % Au-2.5 wt % Pd catalyst supported on TiO₂— acid-treated and water treated—followed by calcinations in air at 400° C. for 3 hrs. The following results were obtained:

Produc- Pre- Temper- tivity treatment ature/ Mol/ Catalyst of support Solvent ° C. kg_(cat)-h 2.5-2.5%Au—Pd/ Water Water + Methanol 2 64 TiO₂ 2.5-2.5%Au—Pd/ Water Water + Methanol 20 25 TiO₂ 2.5-2.5%Au—Pd/ Water Water + Methanol 40 10 TiO₂ 2.5-2.5%Au—Pd/ 2%HNO₃ Water + Methanol 2 80 TiO₂ 2.5-2.5%Au—Pd/ 2%HNO₃ Water + Methanol 20 100 TiO₂ 2.5-2.5%Au—Pd/ 2%HNO₃ Water + Methanol 40 60 TiO₂ 2.5-2.5%Au—Pd/ 2%HNO₃ Water + Acetone 2 95 TiO₂ 2.5-2.5%Au—Pd/ 2%HNO₃ Water + Acetone 20 125 TiO₂ 2.5-2.5%Au—Pd/ 2%HNO₃ Water + Acetone 40 64 TiO₂

Catalyst testing was performed using a Parr Instruments stainless steel autoclave with a nominal volume of 50 ml and a maximum working pressure of 14 MPa. The autoclave was equipped with an overhead stirrer (0-2000 rpm) and provision for measurement of temperature and pressure. Typically, the autoclave was charged with catalyst (0.01 g unless otherwise stated), solvent (5.6 g MeOH/Acetone and 2.9 g H₂O) purged three times with CO₂ (3 MPa) and then filled with 5% H₂/CO₂ and 25% O₂/CO₂ to give a hydrogen to oxygen ratio of 1:2, at a total pressure of 3.7 MPa at 2° C. Stirring (1200 rpm unless otherwise stated) was started on reaching the desired temperature, and experiments were run for 30 min unless otherwise stated. H₂O₂ yield was determined by titration of aliquots of the final filtered solution with acidified Ce(SO₄)₂ (7×10⁻³ mol/l). Ce(SO₄)₂ solutions were standardised against (NH₄)₂Fe(SO₄)₂.6H₂O using ferroin as indicator.

The reaction medium may comprise other components which contribute to a desired result or avoid an undesired result. For example, hydrogen bromide may be added to reduce the tendency for H₂O formation at higher temperatures, causing an increase in yield due to decreased decomposition (thus stabilisation) of the H₂O₂. Addition of HCl and HNO₃ will induce the same stabilisation. However, the presence of halides, and the effect of acid on stainless steel reaction vessels are not desirable in industry. Accordingly, it is assessed by the present inventors that a method of pre-treating a catalyst to induce the same stabilising effect without addition of these corrosive/toxic compounds would be highly desirable.

Although initial trials have been carried out in an autoclave, it is contemplated that it can operate in continuous, or semi-continuous mode. It is envisaged that the process of the invention may be optimised and scaled-up to industrial scale.

The catalysts according to the invention exhibit surprisingly long life and recyclability. The acid washed bi-metallic TiO₂ catalyst has been reused three times and has shown no decrease in activity (See Table 2 below, using 2.5-2.5% Au—Pd catalyst based on acid-washed TiO₂ support)

TABLE 2 Experiment Productivity - Mol/kg_(cat)/hr Initial 110 1^(st) reuse 107 2^(nd) reuse 108 3^(rd) reuse 105

Further initial tests have been undertaken using acid-washed activated carbon supports, after depositing 2.5 wt % Au and 2.5 wt % Pd and heat treating at 400° C. for three hours in air. An untreated carbon support was compared for H₂O₂ productivity (mol/kg_(cat)/hr) with the same carbon washed with varying concentrations of nitric acid. The results are shown in FIG. 1.

The influence of support source, and of the composition of metal particles deposited thereon was assessed, by measuring H₂O₂ productivity for three different silica supports, for Au-only catalysts, Pd-only catalysts and an AuPd catalyst, both without acid washing and after a pre-treatment with 2% nitric acid. The results are shown in FIG. 2. The beneficial effects of acid washing are clear for all supports, and an increase of activity is observed for all catalysts, whether Au only, Pd only or Au and Pd.

FIG. 3 is a comparative test showing that the optimum wt % Au/Pd for non-acid-washed alumina supported catalysts is 4.2% Au:0.8% Pd, or approximately 5.25:1. It is expected that the same proportion will apply in the case of acid-washed supports.

The process according to the invention has, in preliminary trials, demonstrated high yields and/or high selectivity to H₂O₂. Preliminary results for operating the process at or around room temperature indicate that selectivities of greater than 90% can be achieved, and production rates of around 500 mol/kg_(cat)/hr can be achieved when operating under preferred conditions. 

1-10. (canceled)
 11. An H₂O₂ formation catalyst comprising particles of metal selected from the group consisting of gold, palladium and combinations of gold and palladium, deposited on a support which has been acid washed prior to metal deposition.
 12. A catalyst according to claim 11, wherein the particles are the combinations of gold and palladium.
 13. A catalyst according to claim 11, wherein the support is silica, titania, alumina, Fe₂O₃, a zeolite stable under catalyst formation conditions or an activated carbon.
 14. A catalyst according to claim 11, wherein the support has been washed with a dilute nitric acid.
 15. A catalyst according to claim 12, wherein the weight ratio of gold and palladium in the catalyst is approximately 5.25:1.
 16. A method of manufacturing a catalyst, comprising acid washing a catalyst support, depositing a precursor of at least one of gold and palladium onto the acid washed support to form a catalyst precursor and subsequently calcining the catalyst precursor to form a catalyst comprising particles of at least one of gold and palladium deposited on said support.
 17. A process for the formation of H₂O₂ comprising directly reacting oxygen and hydrogen in the presence of a reaction medium and in the presence of a catalyst comprising particles of metal selected from the group consisting of gold, palladium and combinations of gold and palladium, deposited on a support which has been acid washed prior to metal deposition.
 18. A process according to claim 17, wherein the reaction medium comprises a mixture of water and a water-miscible organic solvent.
 19. A process according to claim 18, wherein the reaction medium comprises aqueous methanol.
 20. A process according to claim 17, wherein the reaction temperature is in the range from 2 to 40° C.
 21. A process according to claim 17, wherein the particles are the combinations of gold and palladium.
 22. A process according to claim 17, wherein the support is silica, titania, alumina, Fe₂O₃, a zeolite stable under catalyst formation conditions or an activated carbon.
 23. A process according to claim 17, wherein the catalyst support has been washed with a dilute nitric acid.
 24. A process according to claim 21, wherein the weight ratio of gold and palladium in the catalyst is approximately 5.25:1.
 25. A method of manufacturing a catalyst according to claim 16, wherein the calcining is carried out at a temperature of at least 400° C.
 26. A method of manufacturing a catalyst according to claim 16, wherein the at least one of gold and palladium is both gold and palladium.
 27. A method of manufacturing a catalyst according to claim 16, wherein the support is silica, titania, alumina, Fe₂O₃, a zeolite stable under catalyst formation conditions or an activated carbon.
 28. A method of manufacturing a catalyst according to claim 16, wherein the support has been washed with a dilute nitric acid.
 29. A method of manufacturing a catalyst according to claim 26, wherein the weight ratio of gold and palladium in the catalyst is approximately 5.25:1.
 30. A catalyst according to claim 11, wherein the particles are of gold only.
 31. A catalyst according to claim 11, wherein the particles are of palladium only. 